Preparation of polymers comprising at least one benzo[c][1,2,5]thiadiazol-5,6-dicarbonitrile-unit

Abstract

A polymer containing at least one unit of formula is prepared by treating a compound of formula wherein Y 2 is I, Br, Cl or O—S(O) 2 CF 3 , with an S-donor agent, in order to obtain the compound of formula wherein Y 2 is as defined for the compound of formula (5).

The invention claimed is: 
     
       1. A process for the preparation of a polymer comprising at least one unit of formula 
       
         
           
           
               
               
           
         
         wherein 
         Ar 1  and Ar 2  are independently from each other and at each occurrence C 6-14 -arylene or a 5 to 15 membered heteroarylene, 
         wherein Ar 1  and Ar 2  can be substituted with one to four substituents selected from the group consisting of C 1-30 -alkyl, CN and C 6-14 -aryl, and 
         wherein at least two adjacent Ar 1 , respectively, at least two adjacent Ar 2  can be connected via an -(L) m - linker, 
         wherein L is at each occurrence selected from the group consisting of CR 1 R 2 , C═CR 1 R 2 , C═O and SiR 1 R 2 , wherein R 1  and R 2  are individually from each other and at each occurrence H or C 1-20 -alkyl, and m is 1 or 2, 
         o is an integer from 1 to 8, and 
         n is an integer from 1 to 8, 
         said process comprising 
         (i) treating a compound of formula 
       
       
         
           
           
               
               
           
         
         wherein 
         Y 2  is I, Br, Cl or O—S(O) 2 CF 3 , 
         with an S-donor agent, in order to obtain the compound of formula 
       
       
         
           
           
               
               
           
         
         wherein Y 2  is as defined for the compound of formula (5). 
       
     
     
       2. The process of  claim 1 , wherein in the polymer comprising at least one unit of formula (1)
 Ar 1  and Ar 2  are independently from each other and at each occurrence C 6-10 -arylene or a 5 to 9 membered heteroarylene, 
 wherein Ar 1  and Ar 2  can be substituted with one to four substituents selected from the group consisting of C 1-30 -alkyl, CN and C 6-14 -aryl, and 
 wherein at least two adjacent Ar 1 , respectively, at least two adjacent Ar 2  can be connected via an -(L) m - linker, 
 wherein L is at each occurrence selected from the group consisting of CR 1 R 2 , C═CR 1 R 2 , C═O and SiR 1 R 2 , wherein R 1  and R 2  are individually from each other and at each occurrence H or C 1-20 -alkyl, and m is 1 or 2. 
 
     
     
       3. The process of  claim 2 , wherein in the polymer comprising at least one unit of formula (1)
 Ar 1  and Ar 2  are independently from each other and at each occurrence a 5 to 9 membered heteroarylene, 
 wherein Ar 1  and Ar 2  can be substituted with one to four substituents selected from the group consisting of C 1-30 -alkyl, CN and C 6-14 -aryl, and 
 wherein at least two adjacent Ar 1 , respectively, at least two adjacent Ar 2  can be connected via an -(L) m - linker, 
 wherein L is at each occurrence selected from the group consisting of CR 1 R 2 , C═CR 1 R 2 , C═O and SiR 1 R 2 , wherein R 1  and R 2  are individually from each other and at each occurrence H or C 1-20 -alkyl, and m is 1 or 2. 
 
     
     
       4. The process of  claim 3 , wherein in the polymer comprising at least one unit of formula (1)
 Ar 1  and Ar 2  are independently from each other and at each occurrence a 5 membered heteroarylene, 
 wherein Ar 1  and Ar 2  can be substituted with one to four substituents selected from the group consisting of C 1-30 -alkyl, CN and C 6-14 -aryl. 
 
     
     
       5. The process of  claim 4 , wherein in the polymer comprising at least one unit of formula (1)
 o is an integer from 1 to 6, and 
 n is an integer from 1 to 6. 
 
     
     
       6. The process of  claim 5 , wherein in the polymer comprising at least one unit of formula (1)
 o is an integer from 1 to 4, and 
 n is an integer from 1 to 4. 
 
     
     
       7. The process of  claim 1 , further comprising
 (ii) treating the compound of formula (4) as obtained in step (i) 
 with a compound of formula 
 
       
         
           
           
               
               
           
         
         wherein 
         Ar 1  and o are as defined for the polymer comprising at least one unit of formula (1), and 
         Z b  is selected from the group consisting of B(OZ 1 )(OZ 2 ), SnZ 1 Z 2 Z 3 , 
       
       
         
           
           
               
               
           
         
         wherein Z 1 , Z 2 , Z 3 , Z 4 , Z 5  and Z 6  are independently from each other and at each occurrence H or C 1-6 -alkyl, 
         in the presence of catalyst II, 
         in order to obtain a compound of formula 
       
       
         
           
           
               
               
           
         
         wherein 
         Ar 1  and o are as defined for the polymer comprising at least one unit of formula (1), and 
         (iii) treating a compound of formula (3) as obtained in step (ii) with a Y 1 -donor agent, wherein Y 1  is I, Br, Cl or O—S(O) 2 CF 3 , in order to obtain the compound of formula 
       
       
         
           
           
               
               
           
         
         wherein 
         Ar 1  and o are as defined for the polymer comprising at least one unit of formula (1), and 
         Y 1  is at each occurrence I, Br, Cl or O—S(O) 2 CF 3 , 
         (iv) treating a compound of formula (2) as obtained in step (iii) with a compound of formula 
       
       
         
           
           
               
               
           
         
         wherein 
         Ar 2  and n are as defined for the polymer comprising at least one unit of formula (1), and 
         Z a  is at each occurrence selected from the group consisting of B(OZ 1 )(OZ 2 ), SnZ 1 Z 2 Z 3 , 
       
       
         
           
           
               
               
           
         
         wherein Z 1 , Z 2 , Z 3 , Z 4 , Z 5  and Z 6  are independently from each other and at each occurrence H or C 1-6 -alkyl, 
         in the presence of catalyst I, 
         in order to obtain the polymer comprising at least one unit of formula (1). 
       
     
     
       8. A process for the preparation of a compound of 
       
         
           
           
               
               
           
         
         wherein Y 2  is I, Br, Cl or O—S(O) 2 CF 3 , 
         said process comprising 
         treating a compound of formula 
       
       
         
           
           
               
               
           
         
         wherein 
         Y 2  is as defined for the compound of formula (4) 
         with an S-donor agent. 
       
     
     
       9. The compound of 
       
         
           
           
               
               
           
         
         wherein Y 2  is I, Br, Cl or O—S(O) 2 CF 3 .